Composite and manufacturing method therefor

ABSTRACT

This invention provides a composite having a hydrophilic film made of amorphous titanium oxide. A film is deposited on a substrate made of, for example, glass or synthetic resin. The film is composed of amorphous titanium oxide partially having structures in which a network of Ti—O—Ti bond is broken to give Ti—OH bond terminals.

This application is a divisional of application Ser. No. 09/940,409,filed on Aug. 27, 2001, now U.S. Pat. No. 6,472,088B 2, issued Oct. 29,2002.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a composite in which a film mainly comprisingamorphous titanium oxide is formed on a surface of a base and to amanufacturing method therefor.

2. Description of the Prior Art

It has been known that a base surface is coated with titanium oxide andphotoexcited to make the surface hydrophilic. In the prior art, amongtitanium oxides, only anatase-type titanium dioxide has been madeadequately hydrophilic by photoexcitation.

BRIEF SUMMARY OF THE INVENTION Object of the Invention

Formation of anatase-type titanium dioxide films requires a hightemperature process, which has made it difficult to apply such a film toa base comprising a low melting temperature material such as syntheticresin. For the base made of soda-glass, a high temperature processcauses diffusion of sodium in the soda glass into the titanium dioxidefilm, leading to deteriorated performance (reduction in photoexcitationefficiency). For preventing performance deterioration, it is necessaryto form a passivation layer between the soda-glass base and the titaniumdioxide film, leading to a more complicated manufacturing method.

In view of these problems, an objective of this invention is to providea composite in which a novel amorphous titanium oxide film is depositedon a base surface for hydrophilicity and a manufacturing methodtherefor.

SUMMARY OF THE INVENTION

This invention provides a composite comprising a base and a film mainlyformed of amorphous titanium oxide on the base, wherein the amorphoustitanium oxide partially has a structure in which a network of Ti—O—Tibond is broken to give Ti—OH bond terminals. In general, it is knownthat amorphous titanium oxide films have photoexcitation efficiency toolow to give adequate hydrophilicity. In contrast, our experiments showedthat more hydrophilicity could be achieved by photoexcitation using theamorphous titanium oxide film of this invention partially comprising astructure in which a network of Ti—O—Ti bond is broken to give Ti—OHbond terminals. It may be because in a common amorphous titanium oxidefilm, electrons and holes generated by photoexcitation might have a highprobability of being recombined due to, for example, the presence ofdangling bonds in the film, leading to reduced photoexcitationefficiency, while in a titanium oxide film according to this invention,dangling bonds in the film might be bound to OH groups to reduce thenumber of dangling bonds so that recombination of electrons and holesgenerated by photoexcitation might be inhibited and, furthermore,electron-releasing property of an OH group itself might contribute toimprovement in hydrophilicity.

In amorphous titanium oxide in this invention, a proportion may widelyvary for Ti—OH terminals generated by bond cleavage in Ti—O bonds in aTi—O—Ti bond network. If the proportion is less than 5%, hydrophilicitywill become too low while if the proportion is more than 30%, filmstrength will be reduced. Thus, the most suitable proportion is about 5to 30%. A base may be made of, for example, glass or synthetic resin.When a base is used as a mirror such as an exterior rear view mirror foran automobile and a mirror for a bath room, the mirror may comprise abase made of a transparent material such as glass and synthetic resin; atransparent film; and a reflecting film formed on the rear surface ofthe base. In another configuration, a film may be transparent and areflecting film may be formed between a base made of, e.g., glass orsynthetic resin and the transparent film.

A composite according to this invention may be manufactured by a methodwherein a film in the composite is formed by a plasma CVD technique,comprising the steps of placing a base in a vessel, generating plasma inreduced-pressure oxygen atmosphere in the vessel, and introducing atitanium-containing material in the region where excited speciesattributed to the plasma exist to deposit a film mainly comprisingamorphous titanium oxide on a surface of the base. According to themethod, a film mainly comprising amorphous titanium oxide may bedeposited in a relatively-low temperature process, allowing use of amaterial with a low melting point such as synthetic resin as a base.Furthermore, even when using soda glass as a base, a film may be formedin a relatively-low temperature process so that diffusion of sodium inthe soda glass into the film may be inhibited, resulting in eliminationof the need for a passivation layer and achievement of a simplifiedmanufacturing method. When a content of OH groups in a film isrelatively large, a refractive index is reduced as compared withcrystalline titanium dioxide, allowing reduction in surface reflectionof the film. It may also reduce deterioration in visibility due to adouble image which is cased when a mirror is fabricated using thecomposite of this invention.

In the manufacturing method according to this invention, thetitanium-containing material may be, for example, one mainly comprisingtitanium alkoxide. Such a titanium alkoxide material may mainly comprisea material selected from the group consisting of titaniumtetraisopropoxide {Ti(OC₃H₇)₄}, titanium tetraethoxide {Ti(OC₂H₅)₄}, andtitanium tetrabutoxide {Ti(OC₄H₉)₄}. During deposition of the film onthe base surface, the base may be, for example, at room temperature to150° C. The film may be deposited while allowing ions in the plasma tocollide with the base, to effectively decompose a stable monomer such astitanium alkoxide.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a longitudinal section illustrating an embodiment of acomposite according to this invention;

FIG. 2 schematically shows a network structure of the film 14 in FIG. 1;

FIG. 3 schematically shows an exemplary configuration of a plasma CVDapparatus used for depositing the film 14 in FIG. 1;

FIG. 4 is a section taken along a line A—A in FIG. 3;

FIG. 5 shows the results of analysis of the film 14 according to thisinvention by FT-IR;

FIG. 6 shows the results of analysis of the film 14 according to thisinvention by XRD;

FIG. 7 shows hydrophilic property of the film 14 according to thisinvention;

FIG. 8 schematically shows another example of a configuration for aplasma CVD apparatus used for depositing the film 14 in FIG. 1;

FIG. 9 schematically shows a further example of a configuration for aplasma CVD apparatus used for depositing the film 14 in FIG. 1;

FIG. 10 is a longitudinal section showing an embodiment where acomposite according to this invention is used as an anti-fog mirror(rear surface mirror); and

FIG. 11 is a longitudinal section showing an embodiment where acomposite according to this invention is used as an anti-fog mirror(front surface mirror).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

An embodiment of this invention will be described below. FIG. 1 is alongitudinal section (the film is drawn with an enlarged thickness)illustrating an embodiment of a composite according to this invention. Acomposite 10 is composed of a base (substrate) 12 and a film 14deposited on the base surface. The substrate 12 is a plate made of, forexample, synthetic resin or glass. The film 14 is mainly composed ofamorphous titanium oxide {TiO_(x)(x>2)}.

FIG. 2 schematically shows the structure of the film 14. Titaniumdioxide, either crystal or amorphous, has a basic structure where Ti ispositioned at the center of an octahedron and an oxygen atom ispositioned at each of six apices. The basic structures are mutuallyconnected, sharing two edges for rutile and four edges for anatase. Forthe crystal type, the connection is regular in a wide range, while it isirregular for the amorphous type. In the film 14, connections betweenthe basic structures of titanium oxide (based on titanium dioxide inFIG. 2) (a Ti—O—Ti bond network) are frequently cleaved, and Ti is boundto OH to form a terminal Ti—OH bond at many of the cleavage positions.Titanium dioxide is designated as TiO₂ because O is shared between thebasic structures, while in the structure illustrated in FIG. 2, unsharedoxygen atoms exist at the cleavage positions in the form of Ti—OH andthus TiO_(x) is used to represent the whole composition (x>2; forexample, x=2.3). A proportion of terminal Ti—OH bonds may be mostsuitably 5 to 30% of the whole Ti—O bonds in the connection between thebasic structures.

A method for manufacturing the composite 10 in FIG. 1 will be described.FIG. 3 shows an exemplary configuration of a plasma CVD apparatus usedfor depositing the film 14. FIG. 4 is a section taken along line A—A inFIG. 3. A whole cylindrical vacuum vessel 16 is an anode. The outersurface of the vacuum vessel 16 is wrapped with a heater 18. In thevacuum vessel 16, a quartz tube 20, a cathode 22, and a quartz tube 24are concentrically disposed in sequence. The outer quartz tube 20 isprovided for ensuring insulation between the anode 16 and the cathode22, while the inner quartz tube 24 is provided not only for preventingcontamination of the anode 16 and the cathode 22 but also for supportingthe substrate 12. On the central axis in the vacuum vessel 16, amaterial gas introducing pipe 28 is disposed in such a way that it issupported on the inner quartz tube 24 by a supporting post 30. Thematerial gas introducing pipe 28 is electrically connected to the anode16.

The vacuum vessel 16 is evacuated by a vacuum pump 32 such as a rotarypump. A radio-frequency generator 34 generates a radio-frequency voltagewhich is then applied between the cathode 22 and the anode 16 via amatching box 36. O₂ gas used as a plasma exciting gas is introduced intothe vacuum vessel 16 through a plasma-exciting gas line 40 equipped witha mass flow controller (MFC) 38. Titanium tetraisopropoxide {Ti(OC₃H₇)₄}used as a material monomer is heated in a bubbling cylinder 42. Theheated material monomer is vaporized to give a vapor pressure dependingon the heating temperature. The material gas vaporized by heating is fedto the material gas introducing pipe 28 through a material gas feedingline 50 by a difference between a vapor pressure of the material gas anda pressure in the vacuum vessel 16. A material gas 52 is showered towardthe substrate 12 from material gas outlets 28 a placed in a lowersurface near the tip of the material gas introducing pipe 28. When thevapor pressure of the material gas is too low to obtain a desired flowrate of the material gas, a carrier gas may be used. The carrier gas maybe preferably an inert gas such as Ar. The carrier gas is introducedinto the material monomer 48 in the bubbling cylinder 42 through acarrier gas line 46 equipped with an MFC 44 and then into the vacuumvessel 16 while lifting the material gas up. Lifting up the material gasby the carrier gas allows a more amount of the material gas to beintroduced into the vacuum vessel 16.

After reduced-pressure oxygen atmosphere to about 0.1 to 0.001 Torr isformed in the inside of the vacuum vessel 16, a radio-frequency voltageis applied between the cathode 22 and the anode 16 to induce electricdischarge between the cathode 22 and the anode 16 and between thecathode 22 and the material gas introducing pipe 28 which is of the samepotential as the anode 16. The discharge excites O₂ gas moleculesintroduced in the vacuum vessel 16 to generate plasma 54 and, at thistime the material gas outlets 28 a at the tip of the material gasintroducing pipe 28 is located in the region of plasma 54, while thematerial gas 52 is showered from the material gas outlets 28 a into theplasma 54. Thus, the material gas 52 is decomposed by oxygen radicalsand ions constituting the plasma 54 to form precursors such as Ti—O,which are then deposited on the substrate 12. The deposited precursorsare further activated under plasma atmosphere to form a Ti—O—Ti network.Ti(OC₃H₇)₄ contains hydrogen so that it can form Ti—OH in the process offormation of the precursors. The substrate 12 may be maintained at a lowtemperature of about room temperature to 150° C. (e.g., 70° C.) toinhibit dehydration and condensation reaction of Ti—OH so that the film14 as illustrated in FIG. 2 is formed, in which Ti—OH remains in theTi—O—Ti network. Some factors such as plasma density, pressure and amaterial feeding rate may be adjusted to control an amount (rate) of OHgroups in the film 14. When the feeding rate of the material gas 52 isexcessively high relative to the density of the plasma 54, hydrocarbonin the material monomer may be taken into the film 14 without beingdecomposed, leading to formation of the film 14 without adequate Ti—OHformation. On the other hand, when the feeding rate of the material gas52 is excessively low relative to the density of the plasma 54,probability of collision between the excited species in the plasma 54and the material gas molecules is increased, leading to excessiveacceleration of Ti—O—Ti bond formation and thus to reduction in theamount of the remaining Ti—OH. It is, therefore, necessary to maintainan appropriate relationship between the feeding rate of the material gas52 and density of the plasma 54

The results of analysis of the film 14 deposited by the above plasma CVDprocess will be described. FIG. 5 shows the results of analysis of thecontained molecules by FT-IR (Fourier transform infraredspectrophotometer). Characteristic curve A is a spectrum for a crystaltype titanium dioxide film deposited by sputtering, where sharp Ti—O—Tivibration peaks are seen at 397 cm⁻¹ and 507 cm⁻¹ and no noticeablepeaks corresponding to OH are present. Characteristic curve B is aspectrum for the film 14 according to this invention, where a large peakderived from OH is seen at about 3300 cm⁻¹, indicating that many OHgroups are present in the film 14. Furthermore, broad peaks derived froma Ti—O bond are present near 650 cm⁻¹ and 850 cm⁻¹, indicating that thefilm 14 has a more distorted structure than that in the sputtered film.It is related to the fact that the Ti—O—Ti network is partially cleavedand the cleaved parts have OH terminals.

FIG. 6 shows the results of analysis for crystallinity by XRD (X-raydiffractometer). Characteristic curve C is a spectrum for the film 14according to this invention, where no noticeable peaks for crystallinetitanium dioxide are seen. A broad peak near 33° is derived from asample holder. Characteristic curve D is a spectrum after baking thesample exhibiting characteristic curve C at 800° C., indicatingappearance of (101) and (004) peaks from anatase type and a (211) peakfrom rutile type. These results demonstrate that the film 14 accordingto this invention is amorphous. FIG. 7 shows hydrophilic property of thefilm 14 according to this invention. The hydrophilic property is betterthan that of the rutile type and comparable to that of the anatase type.The hydrophilicity-recovering property in FIG. 7 may indicate aphotocatalyst effect, i.e., an effect of decomposing and removinghydrophobic materials absorbed on the surface of the film 14.

FIG. 8 shows another example of a configuration for a plasma CVDapparatus used for depositing the film 14 (a supporting mechanism foreach part is not shown.). A whole vacuum vessel 56 constitutes an anode.From the top of the vacuum vessel 56, a quartz tube 57 is verticallyinserted and the outer surface of the quartz tube 57 is wrapped with acathode 58. Into the quartz tube 57, O₂ gas used as a plasma excitinggas is fed from an external source. The lower end 57 a of the quartztube 57 is opened in the vacuum vessel 56 and O₂ gas fed to the quartz57 is showered into the vacuum vessel 56 from the lower end 57 a. Belowthe lower end 57 a of the quartz tube 57, a substrate 12 is horizontallydisposed. An annular material gas introducing pipe 60 is horizontallydisposed between the lower end 57 a of the quartz tube 57 and thesubstrate 12. To the material introducing pipe 60, a material gas suchas titanium tetraisopropoxide {Ti(OC₃H₇)₄} or a mixture of the materialgas and a carrier gas such as Ar is fed from an external source, and thematerial gas 64 is showered from a plurality of material gas outlets 60a separated with a circumferentially equal interval in a slightly innerarea in the bottom surface of the pipe 60. The inside of the vacuumvessel 56 is evacuated by a vacuum pump 66 such as a rotary pump. Aradio-frequency generator 68 generates a radio-frequency voltage, whichis applied between the cathode 58 and the anode 56.

After forming an oxygen atmosphere to about 0.1 to 0001 Torr in thevacuum vessel 56, a radio-frequency voltage is applied between thecathode 58 and the anode 56 to induce electric discharge between thecathode 58 and the anode 56. The discharge excites O₂ gas moleculesintroduced in the vacuum vessel 56 to generate plasma 70, which passesthrough the ring center of the material gas introducing pipe 60. Thematerial gas 64 is showered from material gas outlets 60 a of thematerial gas introducing pipe 60 toward a diagonally lower part of thering inside (i.e., toward the plasma 70 and the substrate 12). Thus, thematerial gas 64 is decomposed by oxygen radicals and ions constitutingthe plasma 70 to form precursors such as Ti—O, which are then depositedon the substrate 12. The deposited precursors are further activatedunder the plasma atmosphere to form a Ti—O—Ti network. Ti(OC₃H₇)₄contains hydrogen so that it can form Ti—OH in the process of formationof the precursors. The substrate 12 may be maintained at a lowtemperature of about room temperature to 150° C. (e.g., 70° C.) toinhibit dehydration and condensation reaction of Ti—OH so that the film14 as illustrated in FIG. 2 is formed, in which Ti—OH remains in theTi—O—Ti network. Some factors such as plasma density, pressure and amaterial feeding rate may be adjusted to form the film 14 in which anappropriate amount of Ti—OH remains. Using the plasma CVD apparatus asillustrated in FIG. 8, enhanced oxygen gas is showered toward thesubstrate 12 so that not only radicals but also ions in the plasma 70may collide with the substrate 12 to effectively decompose a stablemonomer such as Ti(OC₃H₇)₄.

FIG. 9 shows a further example of a configuration for a plasma CVDapparatus used for depositing the film 14 (a supporting mechanism foreach part is not shown). In a vacuum vessel 72, an anode 74 and acathode 76 are positioned facing each other. On a surface of the cathode76 facing the anode 74, a substrate 12 is held. Into the vacuum vessel72, a mixture of O₂ gas used as a plasma exciting gas and a material gassuch as titanium tetraisopropoxide {Ti(OC₃H₇)₄} are supplied fromexternal sources. The vacuum vessel 72 is evacuated by a vacuum pump 78such as a rotary pump. A radio-frequency generator 80 generates aradio-frequency voltage, which is applied between the cathode 76 and theanode 74. There is inserted a capacitor 82 between the radio-frequencygenerator 80 and the cathode 76.

After forming an oxygen atmosphere to about 0.1 to 0.001 Torr in thevacuum vessel 72, a radio-frequency voltage is applied between thecathode 76 and the anode 74 to induce electric discharge between thecathode 76 and the anode 74. The discharge excites O₂ gas molecules togenerate plasma 84. The material gas is decomposed by oxygen radicalsand ions constituting the plasma 84 to form precursors such as Ti—O,which are then deposited on the substrate 12. The deposited precursorsare further activated under the plasma atmosphere to form a Ti—O—Tinetwork. Ti(OC₃H₇)₄ contains hydrogen so that it can form Ti—OH in theprocess of formation of the precursors. The substrate 12 may bemaintained at a low temperature of about room temperature to 150° C.(e.g., 70° C.) to inhibit dehydration and condensation reaction of Ti—OHso that the film 14 as illustrated in FIG. 2 is formed, in which Ti—OHremains in the Ti—O—Ti network. Some factors such as plasma density,pressure and a material feeding rate may be adjusted to form the film 14in which an appropriate amount of Ti—OH remains. Using the plasma CVDapparatus as illustrated in FIG. 9, a negative self-bias voltage isapplied to the cathode 76 by the action of the capacitor 82 inserted onthe side of the cathode 76. Thus, oxygen cations 85 in the plasma 84 maycollide with the substrate 12 to effectively decompose a stable monomersuch as Ti(OC₃H₇)₄.

FIGS. 10 and 11 show an embodiment where a composite according to thisinvention is used as an anti-fog mirror such as an automobile exteriorrear view mirror and a bath mirror. An anti-fog mirror 86 in FIG. 10 isconstructed as a rear surface mirror, where a reflection film 88 madeof, for example, Cr or Al is deposited on the rear surface of thesubstrate 12 in the composite 10 in FIG. 1. The reflecting film 88 maybe deposited before or after deposition of the film 14. An anti-fogmirror 90 in FIG. 11 is constructed as a front surface mirror, where areflecting film 92 is disposed between the substrate 12 and the film 14in the composite 10 in FIG. 1. The reflecting film 88 may be depositedbefore deposition of the film 14.

These embodiments have been described as using titaniumtetraisopropoxide {Ti(OC₃H₇)₄} as a starting material, but othertitanium alkoxides such as titanium tetraethoxide {Ti(OC₂H₅)₄} andtitanium tetrabutoxide {Ti(OC₄H₉)₄} may be also used as a startingmaterial. In these embodiments, a film 14 is deposited directly on asubstrate 12 or a reflecting film 92, but in this invention, anotherfunctional film may be separately formed between the substrate 12 or thereflecting film 92 and the film 14. A film 14 is formed as the topsurface in these embodiments, but, in this invention, another functionalfilm may be formed on the film 14 as long as adequate hydrophilicityrequired in this invention is provided. These embodiments have aconfiguration that in the film 14, connections between the basicstructures of the titanium oxide (a Ti—O—Ti bond network) are frequentlycleaved and in many of the cleavage positions Ti is bound to OH to forma terminal Ti—OH bond, but in this invention, there may exist a moietywhere at a cleavage position Ti is bound to an atom or group other thanOH as long as adequate hydrophilicity required in this invention isprovided. The film in this invention may contain substances other thanamorphous titanium oxide as long as adequate hydrophilicity required inthis invention is provided.

What is claimed is:
 1. A method for manufacturing a composite comprisinga base and a film mainly formed of amorphous titanium oxide on the base,wherein the amorphous titanium oxide partially has a structure in thefilm in which a network of Ti—O—Ti bonds are broken to give terminalTi—OH bonds, said method comprising the steps of placing a base in avessel, generating plasma in reduced-pressure oxygen atmosphere in saidvessel, and introducing a titanium-containing material in the regionwhere excited species attributed to the plasma exist to deposit a filmmainly comprising amorphous titanium oxide on a surface of said base. 2.The method for manufacturing the composite according to claim 1, whereinsaid titanium-containing material mainly comprises titanium alkoxide. 3.The method for manufacturing the composite according to claim 2, whereinsaid titanium alkoxide mainly comprises a material selected from thegroup consisting of titanium tetraisopropoxide (Ti(OC₃H₇)₄), titaniumtetraethoxide (Ti(OC₂H₅)₄), and titanium tetrabutoxide (Ti(OC₄H₉)₄). 4.The method for manufacturing the composite according to claim 1, whereinduring deposition of said film on said base surface, the base is at roomtemperature to 150° C.
 5. The method for manufacturing the compositeaccording to claim 1, wherein said film is deposited while ions in saidplasma are colliding with said base.